Pre-deposition treatment for FET technology and devices formed thereby

ABSTRACT

Embodiments disclosed herein relate to a pre-deposition treatment of materials utilized in metal gates of different transistors on a semiconductor substrate. In an embodiment, a method includes exposing a first metal-containing layer of a first device and a second metal-containing layer of a second device to a reactant to form respective monolayers on the first and second metal-containing layers. The first and second devices are on a substrate. The first device includes a first gate structure including the first metal-containing layer. The second device includes a second gate structure including the second metal-containing layer different from the second metal-containing layer. The monolayers on the first and second metal-containing layers are exposed to an oxidant to provide a hydroxyl group (—OH) terminated surface for the monolayers. Thereafter, a third metal-containing layer is formed on the —OH terminated surfaces of the monolayers on the first and second metal-containing layers.

PRIORITY CLAIM AND CROSS-REFERENCE

This application is a divisional of U.S. application Ser. No.15/992,556, filed on May 30, 2018, now U.S. Pat. No. 10,504,789, whichis hereby incorporated herein by reference.

BACKGROUND

When fabricating field effect transistors (FETs), such as fin-like FETs(FinFETs), device performance can be improved by using a metal gateelectrode instead of a polysilicon gate electrode. Formation of themetal gate electrode may include sequentially forming a gate dielectriclayer, a barrier layer, a work function layer, and a metal liner layerin a high aspect ratio trench, followed by the trench filling with agate material. The work function layer may use different materials fordifferent types of transistors, such as p-type FinFET or n-type FinFET,to fine tune threshold voltage (Vt) of the transistor and thus enhancedevice electrical performance as needed. However, with the decreasing inscaling, new challenges are presented.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIGS. 1A and 1B illustrate a flow chart illustrating an exemplary methodfor fabricating a semiconductor device according to some embodiments.

FIGS. 2 through 4 are perspective views of a portion of thesemiconductor device corresponding to various stages of fabricationaccording to some embodiments.

FIGS. 5 through 11 are schematic cross-sectional views of a portion ofthe semiconductor device corresponding to various stages of fabricationaccording some embodiments.

FIG. 12 illustrates a simplified semiconductor device at an intermediatestage of processing showing portions of gate structures in three deviceregions.

FIG. 13 illustrates a simplified semiconductor device at an intermediatestage of processing according to some embodiments.

FIGS. 14A to 14C show XPS spectra of TiAlC deposited on differentsubstrates according to some embodiments.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the provided subjectmatter. Specific examples of components and arrangements are describedbelow to simplify the present disclosure. These are, of course, merelyexamples and are not intended to be limiting. For example, the formationof a first feature over or on a second feature in the description thatfollows may include embodiments in which the first and second featuresare formed in direct contact, and may also include embodiments in whichadditional features may be formed between the first and second features,such that the first and second features may not be in direct contact. Inaddition, the present disclosure may repeat reference numerals and/orletters in the various examples. This repetition is for the purpose ofsimplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

The present disclosure is generally related to semiconductor devices,and more particularly to a pre-treatment of work function materialsutilized in metal gates of different types of transistors on a samesemiconductor substrate. Generally, the pre-treatment passivates asurface of the work function materials with a monolayer, such as amonolayer of aluminum oxide or silicon oxide. The pre-treatment mayensure the layer subsequently deposited on the passivated surface of thework function materials will have a more uniform thickness in the metalgates of different types of transistors, allowing minimized impacts onthe gap-filling performance and/or threshold voltage (Vt) of otherlayers in the metal gate. Other embodiments include methods of multi-Vttuning for n-type or p-type devices by providing different or distinctmetal layer between a work-function tuning layer and a gate dielectriclayer for different device regions of a FET, such as an n-FET or p-FETdevice. The distinct metal layer can affect the composition andthickness of the work-function tuning layer, thereby changing the workfunction value of the work-function tuning layer deposited thereon. Thedistinguished work-function tuning layers on different substratesprovide different n-type work functions for the purpose of multi-Vttuning without stacking multilayers of the metal layer. As a result,more space can be provided for metal gate filling.

The foregoing broadly outlines some aspects of embodiments described inthis disclosure. It is contemplated that the pre-treatment process maybe implemented for a planar transistor device or for a three-dimensionaltransistor device, such as the semiconductor device 201 described inthis disclosure. Some example devices for which aspects described hereinmay be implemented include fin field effect transistors (FinFETs),Horizontal Gate All Around (HGAA) FETs, Vertical Gate All Around (VGAA)FETs, nanowire channel FETs, strained-semiconductor devices,silicon-on-insulator (SOI) devices, or other devices that can bebeneficial from the pre-treatment process to mitigate the issuesassociated with loading effect and/or substrate-dependent growth.

FIGS. 1A and 1B illustrate a flow chart 100 illustrating an exemplarymethod for fabricating a semiconductor device 201 according to variousembodiments of the present disclosure. FIGS. 2 through 4 are perspectiveviews and FIGS. 5 through 11 are schematic cross-sectional views of aportion of the semiconductor device corresponding to various stages offabrication according to the flow chart of FIGS. 1A and 1B. It is notedthat the flow chart 100 may be utilized to form any other semiconductorstructures not presented herein. Those skilled in the art shouldrecognize that the full process for forming a semiconductor device andthe associated structures are not illustrated in the drawings ordescribed herein. Although various operations are illustrated in thedrawings and described herein, no limitation regarding the order of suchsteps or the presence or absence of intervening steps is implied.Operations depicted or described as sequential are, unless explicitlyspecified, merely done so for purposes of explanation without precludingthe possibility that the respective steps are actually performed inconcurrent or overlapping manner, at least partially if not entirely.

The flow chart 100 begins at operation 102 by providing a substrate 200having a gate structure 212 formed over a plurality of fins 202 formedon the substrate 200, as shown in FIG. 2. The substrate 200 may be orinclude a bulk semiconductor substrate, a semiconductor-on-insulator(SOI) substrate, or the like, which may be doped (e.g., with a p-type oran n-type dopant) or undoped. In some embodiments, the semiconductormaterial of the semiconductor substrate may include an elementalsemiconductor including silicon (Si) or germanium (Ge); a compoundsemiconductor; an alloy semiconductor; or a combination thereof. Othersubstrates may be used.

Each fin 202 provides an active region where one or more devices areformed. The fins 202 are fabricated using suitable processes performedon the substrate 200 including masking, photolithography, and/or etchprocesses, to form trenches 214 into the substrate 200, leaving thefins, such as the fins 202, extended upwardly from the substrate 200.The fins 202 may be patterned by any suitable method. For example, thefins 202 may be patterned using one or more photolithography processes,including double-patterning or multi-patterning processes. Generally,double-patterning or multi-patterning processes combine photolithographyand self-aligned processes, allowing patterns to be created that have,for example, pitches smaller than what is otherwise obtainable using asingle, direct photolithography process. For example, in someembodiments, a sacrificial layer is formed over a substrate andpatterned using a photolithography process. Spacers are formed alongsidethe patterned sacrificial layer using a self-aligned process. Thesacrificial layer is then removed, and the remaining spacers may then beused to pattern the fins 202 and form the trenches 214.

The trenches 214 may then be filled with an insulating material such asan oxide (e.g., silicon oxide), a nitride, the like, or a combinationthereof by an appropriate deposition technique. Other insulatingmaterials formed by any acceptable process may be used. The insulatingmaterial may be recessed, such as by using an acceptable etch process,to form the isolation regions 216. The insulating material is recessedsuch that the fins 202 protrude above and from between neighboringisolation regions 216.

The isolation regions 216 can separate the semiconductor device 201 intovarious device regions. In the example as shown, the semiconductordevice 201 includes a first device region 250 a and a second deviceregion 250 b. One or more devices may be formed in the first deviceregion 250 a, and one or more devices may be formed in the second deviceregion 250 b. For example, each of the device regions 250 a, 250 b mayinclude a type of devices, such as p-type devices or n-type devices, andfurther, the characteristics of devices may vary within each of thedevice regions 250 a, 250 b. In some embodiments, the semiconductordevice 201 may be a multi-threshold voltage IC device utilized tooptimize delay or power, for example. In such a case, the devices in thedevice regions 250 a, 250 b may be any combination of an n-typeultra-low threshold voltage (N-uLVT) device, an n-type low thresholdvoltage (N-LVT) device, an n-type standard threshold voltage (N-SVT), ann-type high threshold voltage (N-HVT) device, a p-type ultra-lowthreshold voltage (P-uLVT) device, a p-type low threshold voltage(P-LVT) device, a p-type standard threshold voltage (P-SVT), a p-typehigh threshold voltage (P-HVT) device, or any combination thereof. Forexample, an n-type device, such as an n-type FinFET device, can be inthe first device region 250 a, and may be an N-SVT device, while anothern-type device can be in the second device region 250 b and may be anN-uLVT device. However, it is contemplated that a person having ordinaryskill in the art may employ in the device regions any type of devices,and further, may employ any number of metal gates, each including any ofa variety of different types of work-function tuning layer (to bedescribed below) and/or combination of layers to achieve a desiredmultiple threshold voltage scheme.

Dummy gate structures 212 are then formed over the fins 202. The dummygate structures 212 each includes an interfacial dielectric 206, a dummygate 208, and a mask 210. The interfacial dielectric 206, dummy gate208, and mask 210 for the dummy gate structures 212 may be formed bysequentially forming respective layers, and then patterning those layersinto the dummy gate structures 212. For example, a layer for theinterfacial dielectrics 206 may include or be silicon oxide, siliconnitride, the like, or multilayers thereof, and may be thermally and/orchemically grown on the fins 202, or conformally deposited, such as byplasma enhanced chemical vapor deposition (PECVD), atomic layerdeposition (ALD), or any suitable deposition technique. A layer for thedummy gates 208 may include or be silicon (e.g., polysilicon) or anothermaterial deposited by chemical vapor deposition (CVD), physical vapordeposition (PVD), or any suitable deposition technique. A layer for themask 210 may include or be silicon nitride, silicon oxynitride, siliconcarbon nitride, the like, or a combination thereof, deposited by CVD,PVD, ALD, or any suitable deposition technique. The layers for the mask210, dummy gates 208, and interfacial dielectrics 206 may then bepatterned, for example, using photolithography and one or more etchprocesses, to form the mask 210, dummy gate 208, and interfacialdielectric 206 for each dummy gate structure 212.

At operation 104, gate spacers 220 are formed along sidewalls of thegate structure 212 (e.g., sidewalls of the interfacial dielectrics 206,dummy gates 208, and masks 210) and over the fins 202. The gate spacers220 may be formed by conformally depositing one or more layers for thegate spacers 220 and anisotropically etching the one or more layers, forexample. The one or more layers for the gate spacers 220 may include amaterial different from the material(s) for the gate structure 212. Inone embodiment, the gate spacer 220 may include or be a dielectricmaterial, such as silicon oxygen carbide, silicon nitride, siliconoxynitride, silicon carbon nitride, the like, multi-layers thereof, or acombination thereof, and may be deposited by CVD, ALD, or any suitabledeposition technique. An anisotropic etching process, such as a RIE,NBE, or any suitable etch process, is then performed to remove portionsof the spacer layers to form the gate spacer 220, as depicted in FIG. 3.

After the gate spacer 220 is formed, source/drain regions 213 a, 213 bmay be formed in the fins 202. In some examples, recesses can be etchedin the fins 202 using the dummy gate structures 212 as masks (such thatrecesses are formed on opposing sides of the dummy gate structures 212),and an epitaxial material may be epitaxially grown in the recesses toform the source/drain regions 213 a, 213 b. Additionally oralternatively, the source/drain regions 213 a, 213 b may be formed byimplanting dopants into the fins 202 and/or the epitaxial source/drainregions using the dummy gate structures 212 as masks (such that thesource/drain regions are formed on opposing sides of the dummy gatestructures 212).

Subsequently, an interlayer dielectric (ILD) 218 is formed over thesubstrate 200 and on the gate spacer 220. In some embodiments, thesemiconductor device 201 may further include a contact etch stop layer(not shown) underneath the ILD 218 and above the substrate 200 and gatespacer 220. The contact etch stop layer may include or be siliconnitride, silicon carbon nitride, silicon carbon oxide, carbon nitride,the like, or a combination thereof, and may be deposited by CVD, PECVD,ALD, or any suitable deposition technique. The ILD 218 may include or betetraethylorthosilicate (TEOS) oxide, silicon dioxide, a low-kdielectric material (e.g., a material having a dielectric constant lowerthan silicon dioxide), such as silicon oxynitride, phosphosilicate glass(PSG), borosilicate glass (BSG), borophosphosilicate glass (BPSG),undoped silicate glass (USG), fluorinated silicate glass (FSG),organosilicate glasses (OSG), SiO_(x)C_(y), Spin-On-Glass,Spin-On-Polymers, silicon carbon material, a compound thereof, acomposite thereof, the like, or a combination thereof. The ILD 218 maybe deposited by spin-on, CVD, FCVD, PECVD, PVD, or any suitabledeposition technique. A chemical mechanical planarization (CMP) processmay then be performed to planarize the ILD 218 and to remove the masks210 of the dummy gate structures 212, thereby defining a top surface 224that is substantially coplanar with a top surface of the dummy gates 208of the gate structures 212, as shown in FIG. 3.

At operation 106, the gate structures 212 are removed using one or moreetch processes. Upon removal of the gate structures 212, trenches 230are formed to expose at least portions of surfaces 232 of the isolationregions 216, as shown in FIG. 4, and surfaces of channels of the fins202. The trench 230 allows a gate structure, such as a replacement gatestructure, to be formed therein. In some examples, the dummy gates 208exposed through the top surface 224 of the ILD 218 are removed using anetching process, and the interfacial dielectrics 206 are thereafterremoved by a different etching process. The etching processes mayinclude a suitable wet etch, dry (plasma) etch, and/or other suitableprocesses. For example, a dry etching process may usechlorine-containing gases, fluorine-containing gases, other etchinggases, or a combination thereof. The wet etching solutions may includeNH₄OH, HF (hydrofluoric acid) or diluted HF, deionized water, TMAH(tetramethylammonium hydroxide), other suitable wet etching solutions,or combinations thereof. Trenches 230 are therefore formed between thegate spacers 220 where the gate structures 212 are removed, and channelregions of the fins 202 are exposed through the trenches 230.

FIGS. 5 through 11 depict cross-sectional views of the semiconductordevice at further manufacturing stages. The cross-sectional views ofFIGS. 5 through 11 correspond to the cross-section A-A′ in FIG. 4. Thecross-section A-A′ is along the fins 202 and is generally orthogonal toa longitudinal direction of the trenches 230.

At operation 108, layers for replacement gate structures 212 a, 212 bfor the first and second device regions 250 a, 250 b, respectively, areformed in the trenches 230 where the dummy gate structures 212 wereremoved. In the illustrated embodiment, the layers for the replacementgate structures 212 a, 212 b include an interfacial dielectric 240, agate dielectric layer 242, a capping layer 245, and an optional barrierlayer 247 sequentially formed in the trenches 230 between the gatespacers 220 in the first and second device region 250 a, 250 b,respectively, as shown in FIG. 5. The interfacial dielectrics 240 areformed on top and sidewalls surfaces of the fins 202 along the channelregions (defined under the replacement gate structures and between thesource/drain regions). The interfacial dielectric 240 can be, forexample, an oxide (e.g., silicon oxide) formed by thermal or chemicaloxidation of the fins 202, a nitride (e.g., silicon nitride), and/or anysuitable dielectric layer formed by CVD, ALD, molecular beam deposition(MBD), or any suitable deposition technique.

The gate dielectric layer 242 can be conformally deposited in thetrenches 230 on the interfacial dielectric 240, sidewalls of the gatespacers 220 and on the top surfaces of the ILD 218 and the contact etchstop layer (if used). The gate dielectric layer 242 may include or besilicon oxide, silicon nitride, a high-k dielectric material,multilayers thereof, or other suitable dielectric material. A high-kdielectric material may have a k value greater than about 4.0, forexample about 7.0, and may include a metal oxide of or a metal silicateof hafnium (Hf), aluminum (Al), zirconium (Zr), lanthanum (La),magnesium (Mg), barium (Ba), titanium (Ti), lead (Pb), multilayersthereof, or a combination thereof. The gate dielectric layer 242 can bedeposited by ALD, PECVD, MBD, or any suitable deposition technique.

Then, the capping layer 245 and the barrier layer 247 can be conformally(and sequentially) deposited on the gate dielectric layer 242. Thecapping layer 245 and the barrier layer 247 can include a nitride,silicon nitride, carbon nitride, and/or aluminum nitride of tantalumand/or titanium; a nitride, carbon nitride, and/or carbide of tungsten;the like; or a combination thereof; and may be deposited by ALD, PECVD,MBD, or another deposition technique. In some examples, a capping layer245 (e.g., a TiN layer) is formed conformally on the gate dielectriclayer 242; a barrier layer 247 (e.g., a TaN layer) is formed conformallyon the capping layer 245. In some cases, the barrier layer 247 may alsobe or part of a work-function tuning layer. In some examples, thebarrier layer 247 can be omitted. While the capping layer 245 andbarrier layer 247 are each shown as a single layer, it is contemplatedthat one or more barrier layers and/or capping layers is also possibleand can be implemented in any desired order depending upon theapplication and threshold voltage needed for the device.

After the gate dielectric layer 242, the capping layer 245, and thebarrier layer 247 are formed, a work-function tuning layer 244 isconformally formed on the barrier layer 247. The work-function tuninglayer 244 may be or include a single layer of a material or multiplelayers each being a different material. While a single layer of thework-function tuning layer 244 is shown, it is contemplated that thework-function tuning layer 244 may include one or more work functionmaterials, depending on the application and threshold voltage needed forthe device. In the embodiment shown in FIG. 6, the work-function tuninglayer 244 is a work function material formed in both first and seconddevice regions 250 a, 250 b.

A work function value is associated with the material composition of thework-function tuning layer 244. The material of the work-function tuninglayer 244 is chosen to tune its work function value so that a desiredthreshold voltage (Vt) is achieved in the device that is to be formed inthe respective region. Suitable examples of the work function materialfor a p-type device may include TiAlN, TiN, TaN, Ru, Mo, WN, ZrSi₂,MoSi₂, TaSi₂, NiSi₂, WCN, other suitable materials having a workfunction ranging between 4.8 eV and 5.2 eV, or any combination thereof,and suitable examples of the work function material for an n-type devicemay include Ti, Al, TaAl, TaAlC, TIAlC, TiAlO, HfAl, TiAl, TaC, TaCN,TaSiN, Mn, Zr, other suitable materials having a work function rangingbetween 3.9 eV and 4.3 eV, or any combination thereof. In someembodiments, the work-function tuning layer 244 for p-FETs includesrespective layers of TiAlN and TiN, while the work-function tuning layer244 for n-FETs includes respective layers of TiAlC and TiAlO. In somecases, the work-function tuning layer 244 for the n-FETs includesrespective layers of TiAlC and TiN. Any of materials described here canbe deposited in any desired sequence.

The work-function tuning layer 244 may be deposited by ALD, CVD, PECVD,MBD, and/or any other suitable process. In an example depicted herein,the work-function tuning layer 244 is formed using an ALD process at atemperature from about 200° C. to 600° C. The thickness of thework-function tuning layer 244 may be altered and adjusted by alteringprocess parameters during the ALD deposition process, such as the numberof deposition cycles, number of the pulses of precursors, pulsefrequency, substrate temperature, pressure, and the like. It iscontemplated that multiple depositions of various work-function tuninglayers, patterning and etching may be performed to obtain a multiplethreshold voltage scheme.

At operation 110, a patterned mask structure 248 is disposed on thesecond device region 250 b of the semiconductor device 201 of thesubstrate 200, as shown in FIG. 6. The patterned mask structure 248overfills the trench 230 and covers the exposed surface of the seconddevice region 250 b. The patterned mask structure 248 protects the FETin the second device region 250 b from damage during theetching/patterning process, while exposing the first device region 250 aof the semiconductor device 201 for further processing such as etching.In some embodiments, the patterned mask structure 248 may include aphotoresist 254 patterned with a photolithography process and mayfurther include a bottom anti-reflective coating (BARC) 252 filling thetrenches 230 in the device regions 250 b.

At operation 112, an etching process 243 is performed to remove thework-function tuning layer 244 from the trench 230 of the FET in thefirst device region 250 a that is not covered by the patterned maskstructure 248, as shown in FIG. 6. Upon removal of the work-functiontuning layer 244, the barrier layer 247 in the trench 230 of the FET inthe first device region 250 a is exposed. The etching process may be awet etching process performed by immersing or soaking the substrate 200with an etching solution. Alternatively or additionally, a dry process,such as a vapor or a plasma process, may be utilized to remove thework-function tuning layer 244 in the first device region 250 a. In someembodiments, a combination of wet and dry processes may be utilized toremove the work-function tuning layer 244 from the desired locations. Insome examples, the work-function tuning layer 244 is removed from thetrench 230 using a wet process performed such as dipping, immersing, orsoaking the substrate with or in an etching solution in a wet tank. Insuch a case, the etching solution may be an alkaline, neutral or acidsolution with a pH value in a predetermined range, depending on thematerial types of the work-function tuning layer 244 to be removed.

Although the work-function tuning layer 244 is illustrated as one layer,the work-function tuning layer 244 may include multiple layers ofdifferent materials, as described above. Hence, in some examples, it iscontemplated that one or more of the multiple layers of thework-function tuning layer 244 are removed by the etching process 243,while one or more of the multiple layers of the work-function tuninglayer 244 remain after the etching process 243.

At operation 114, after the work-function tuning layer 244 has beenremoved from the trench 230 of the FET in the first device region 250 a,the patterned mask structure 248 is removed from the second deviceregion 250 b, as shown in FIG. 7. The patterned mask structure 248 maybe removed using any suitable process such as resist stripping orashing.

FIG. 7 shows the semiconductor device 201 at an intermediate stage ofprocessing in which the barrier layer 247 in the trench 230 of the FETin the first device region 250 a and the work-function tuning layer 244in the trench 230 of the FET in the second device region 250 b areexposed. In other examples, as indicated previously, a layer of thework-function tuning layer 244 in the trench 230 of the FET in the firstdevice region 250 a and another layer of the work-function tuning layer244 in the trench 230 of the FET in the second device region 250 b areexposed, which layers in the different device regions 250 a, 250 b maybe a different material. Although subsequent description in FIGS. 8through 11 may refer to the barrier layer 247 in the trench 230 of theFET in the first device region 250 a and the work-function tuning layer244 in the trench 230 of the FET in the second device region 250 b, aperson having ordinary skill in the art will readily understand thatsuch description is applicable to different layers of the work-functiontuning layer 244 (e.g., with the different layers being differentmaterials) being in the different device regions 250 a, 250 b.

The surface of the barrier layer 247 and/or the surface of thework-function tuning layer 244 may oxidize due to exposure to anexternal ambient after deposition of the work-function tuning layer. Forexample, the semiconductor device may have been transferred ex-situ toanother processing chamber (e.g., an etch process chamber) of theprocessing system for processing (e.g., for removing the work-functiontuning layer). Oxidation of the barrier layer 247 and the work-functiontuning layer 244, which may contain transition metals (e.g., Ta, Ti,etc.), tend to have hydrogen (—H) terminated surfaces after exposure toan external ambient such as air. However, the barrier layer and thework-function tuning layer 244 having hydrogen terminated surfaces aregenerally less reactive to the subsequent ALD metal liner layerdeposition as compared to hydroxyl group (—OH) terminated surfaces,which in turn can affect the growth rate of the subsequent ALD metalliner layer.

Various embodiments include an in-situ pre-treatment or pre-depositiontreatment process which includes soaking a barrier layer and/or awork-function tuning layer in a reactant agent to provide a treatedsurface for the barrier layer and/or the work-function tuning layerprior to deposition of a metal liner layer by an ALD. The treatedsurface has a monolayer of the reactant formed thereon. The monolayer ofthe reactant is oxidized when exposing to an external ambient such asair or oxidants, leaving the monolayer of the reactant terminated withhydroxyl group (—OH) that can readily react with the subsequent ALD usedto form a metal liner layer. By employing the present pre-treatmentprocess, the work function of the subsequently deposited metal linerlayer may not depend on the quality of an underlying surface (e.g., suchas an underlying work-function tuning layer having an oxidized surfacelayer). In addition, the growth rate of the subsequently deposited metalliner layer may not depend on a varying substrate surface (e.g., of thebarrier layer or work-function tuning layer) that can affect the growthrate (and thus the thickness) of the subsequently deposited metal linerlayer. The pre-treated barrier layer and/or the work-function tuninglayer provide the same treated starting surface for the subsequent ALDof the metal liner layer. As a result, the loading effect for thesubsequent ALD due to substrate dependent growth is mitigated.

At operation 116, a pre-treatment process 253 is performed so thatrespective exposed layers in the trenches 230 of the FETs in the firstdevice region 250 a and in the second device region 250 b are soaked ina reactant agent. The pre-treatment process 253 provides, for theexposed layers, a treated surface 261, 263 having a monolayer 251 of thereactant formed thereon, as shown in FIG. 8. The monolayer of thereactant is later oxidized and forms hydroxyl group (—OH) terminatedsurfaces when exposed to an external ambient such as air or oxidants.The term “soak” may refer to introducing a precursor in the chamber,then closing off the inlets and exhausts for a predetermined time (e.g.,2 seconds to 5 minutes) while the precursor adsorbs or reacts with thesurface a substrate. The term “pre-treatment” may be usedinterchangeably with the terms “surface treatment”, “pre-depositiontreatment”, “pre-deposition soak”, “soak treatment”, or “pre-soak”.

In various embodiments, the reactant agent may include an aluminum-basedprecursor or a silicon-based precursor. Exemplary aluminum-basedprecursors may include, but are not limited to trimethylaluminum (TMA),triethylaluminum (TEA), dimethylethylaminealane (DMEAA),dimethylaluminum hydride (DMAH), tritertiarybutyl aluminium (TrBA),tri-isobutyl-aluminum (TIBA), triimethylylamine alane (TMAA),trimethylamine alane (TEAA), any suitable aluminum-containingmetalorganic precursors, and any combination thereof. Exemplarysilicon-based precursors may include, but are not limited to silanes andorganosilanes. Silanes may include silane (SiH₄), disilane (Si₂H₆),trisilane (Si₃H₈), tetrasilane (Si₄H₁₀), and any combination thereof.Organosilanes may include compounds with the empirical formulaR_(y)Si_(x)H_((2x+2−y)), where R is independently methyl, ethyl, propyl,or butyl, such as methylsilane ((CH₃)SiH₃), dimethylsilane ((CH₃)₂SiH₂),ethylsilane ((CH₃CH₂)SiH₃), methyldisilane ((CH₃)Si₂H₅),dimethyldisilane ((CH₃)₂Si₂H₄), hexamethyldisilane ((CH₃)₆Si₂),tris(dimethylamino)silane (TDMAS), and any combination thereof. In somecases, the silicon-based precursor may be carbon-free.

The aluminum-based precursor and the silicon-based precursor may bechosen because the deposition thickness of a metal liner layer (e.g.,TiN) subsequently deposited by ALD on a silicon-based substrate and analuminum-based substrate after 20 ALD cycles, 40 ALD cycles, and 90 ALDcycles is found to be substantially the same. Hence, providing orpassivating the surfaces of the different layers of the FETs with amonolayer 251 of aluminum or silicon can cause the metal liner layer(e.g., TiN) subsequently deposited by ALD to be formed at the samegrowth rate (and thus the same thickness).

The pre-treatment process 253 may be performed using a chemical vapordeposition process such as ALD, plasma enhanced atomic layer deposition(PEALD), plasma enhanced cyclic CVD (PECCVD), pulsed CVD, or any othersuitable process such as an implantation process. In some embodiments,the pre-treatment process is performed using an ALD soak treatmentprocess. During an ALD soak treatment process, the semiconductor device201 is heated to a temperature above the condensation temperature butbelow the thermal decomposition temperature of a reactant agent (e.g.,Al-based or Si-based precursor). The semiconductor device 201 is thenexposed, soaked, or immersed in the reactant agent so that the reactantis adsorbed and reacted on the surface of the exposed layer in thetrench 230 of the FET in the first device region 250 a and on thesurface of the exposed layer in the trench 230 of the FET in the seconddevice region 250 b. The reactant forms a monolayer 251 of the reactant(e.g., Al monolayer or Si monolayer) on the treated surfaces 261, 263.The semiconductor device 201 is then exposed to air or oxidants to allowspontaneous formation of a native oxide (e.g., aluminum oxide or siliconoxide) on the monolayer of the reactant. Insets 270, 272 in FIG. 8 arepartially enlarged views showing the monolayer 251 of the reactanthaving a hydroxyl group (—OH) termination 265 formed on the barrierlayer 247 and the work-function tuning layer 244, respectively. In theexample shown in FIG. 8, the “R” represents species including aluminum(Al) or silicon (Si).

In some examples, a monolayer of aluminum oxide is formed on the barrierlayer 247 of the FET in the first device region 250 a and on thework-function tuning layer 244 of the FET in the second device region250 b, respectively, by an ALD soak treatment process. The ALD soaktreatment process begins with setting the temperature of thesemiconductor device 201 in a process chamber to a temperature range ofabout 20° C. to about 130° C., for example about 60° C. to about 100° C.An aluminum-based precursor, such as TMA or TEA described above, isintroduced into the process chamber so that the semiconductor device 201is soaked or immersed in the aluminum-based precursor. The TMA or TEAmay be flowed into the process chamber at a flow rate of about 50 sccmto about 8000 sccm, such as about 300 sccm to about 5000 sccm, forexample about 500 sccm to about 2000 sccm. The semiconductor device 201may be soaked or immersed in the TMA or TEA for about 1 second to about300 seconds to form a monolayer of aluminum on the surface of thebarrier layer 247 and the work-function tuning layer 244, respectively.The duration of the soak may be adjusted to obtain a desired amount ofaluminum on and/or in the exposed layer. In some cases, thesemiconductor device 201 is soaked in the TMA or TEA for about 10seconds to about 60 seconds. In some cases, the semiconductor device 201is soaked in the TMA or TEA for about 5 seconds to about 20 seconds. Insome cases, the semiconductor device 201 is soaked in the TMA or TEA forabout 30 seconds to about 120 seconds. In some embodiments, thesemiconductor device 201 is soaked in the TEA flowing at 600 sccm forabout 30 seconds to about 80 seconds. The monolayer of aluminum may havea thickness of about 0.5 Å to about 20 Å, such as about 1 Å to about 10Å, for example, about 2 Å to about 5 Å. After the TMA or TEA hasadsorbed on the surface of the barrier layer 247 and the surface of thework-function tuning layer 244, the ALD control system interrupts orimpedes the flow of the TMA or TEA to the process chamber. Thesemiconductor device 201 is then transferred to another process chamberfor the subsequent deposition of a metal layer. The vacuum is brokenwhen the semiconductor device 201 leaves the process chamber, which canintroduce an oxidant to the monolayer of aluminum, resulting inconversion of aluminum monolayer to a monolayer of aluminum oxide.

In one example, a monolayer of silicon oxide is formed on the barrierlayer 247 of the FET in the first device region 250 a and on thework-function tuning layer 244 of the FET in the second device region250 b, respectively, by an ALD soak treatment process. The ALD soaktreatment process begins with setting the temperature of thesemiconductor device 201 in a process chamber to a temperature range ofabout 20° C. to about 130° C., for example about 60° C. to about 100° C.A silicon-based precursor, such as silanes or disilanes described above,is introduced into the process chamber so that the semiconductor device201 is soaked or immersed in the silicon-based precursor. The silanes ordisilanes may be flowed into the process chamber at a flow rate of about50 sccm to about 8000 sccm, such as about 300 sccm to about 5000 sccm,for example about 500 sccm to about 2000 sccm. The semiconductor device201 may be soaked or immersed in the silanes or disilanes for about 1second to about 300 seconds to form a monolayer of silicon on thesurface of the barrier layer 247 and the work-function tuning layer 244,respectively. In some cases, the semiconductor device 201 is soaked inthe silanes or disilanes for about 10 seconds to about 60 seconds. Insome cases, the semiconductor device 201 is soaked in the silanes ordisilanes for about 5 seconds to about 20 seconds. In some cases, thesemiconductor device 201 is soaked in the silanes or disilanes for about30 seconds to about 120 seconds. In one embodiment, the semiconductordevice 201 is soaked in the silane (SiH₄) for about 15 seconds to about120 seconds. In another embodiment, the semiconductor device 201 issoaked in the disilane (Si₂H₆) for about 15 seconds to about 60 seconds.The monolayer of silicon may have a thickness of about 0.5 Å to about 20Å, such as about 1 Å to about 100 Å, for example about 2 Å to about 5 Å.After the silanes or disilanes has adsorbed on the surface of thebarrier layer 247 and the surface of the work-function tuning layer 244,the ALD control system interrupts or impedes the flow of the silanes ordisilanes to the process chamber. The semiconductor device 201 is thentransferred to another process chamber for the subsequent deposition ofa metal layer. The vacuum is broken when the semiconductor device 201leaves the process chamber, which can introduce an oxidant to themonolayer of silicon, resulting in conversion of silicon monolayer to amonolayer of silicon oxide.

Alternatively or additionally, two or more reactant agents may be usedin an ALD process to produce the aluminum oxide or silicon oxide. Insuch a case, the pre-treatment process is performed by exposing thesemiconductor device 201 alternately and subsequently to pulses of twoor more reactant agents, which pulses may be separated from each otherby evacuation and/or purging of the process chamber. In some cases,after the adsorption of a monolayer of a first reactant agent (e.g.,Al-based or Si-based precursor) on the surfaces of the respectiveexposed layers in the trenches 230 of the FETs in the first deviceregion 250 a and in the second device region 250 b, the semiconductordevice 201 is exposed to a second reactant (e.g., vapor phase H₂O orother oxidants). During exposure with the second reactant, the secondreactant adsorbs on and reacts with available molecules of the firstreactant to form aluminum oxide or silicon oxide on a monolayer scale.This process may be repeated so that the surface layer is grownmonolayer by monolayer until a desired thickness is reached.

In some examples, a monolayer of aluminum oxide is formed on the barrierlayer 247 of the FET in the first device region 250 a and on thework-function tuning layer 244 of the FET in the second device region250 b, respectively, by an ALD process. The ALD process begins withsetting the temperature of the semiconductor device 201 in a processchamber to a temperature range of about 20° C. to about 500 C, forexample about 250° C. to about 500° C. A first reactant agent, such asTMA or TEA discussed above, is pulsed into the process chamber so thatthe semiconductor device 201 is soaked or immersed in the TMA or TEA.The TMA or TEA may be flowed into the process chamber at a flow rate ofabout 10 sccm to about 6000 sccm, such as about 100 sccm to about 3000sccm, for example about 100 sccm to about 3000 sccm. The soak time maybe about 1 second to about 300 seconds to form an aluminum layer at thesurface of the barrier layer 247 and the work-function tuning layer 244,respectively. For example, the soak time may be about 1 seconds to about180 seconds. In some cases, the soak time may be about 5 seconds toabout 120 seconds. In some cases, the soak time may be about 30 secondsto about 60 seconds. The pulse of the first reactant agent is followedby evacuation and/or a purge gas such as an inert gas. The inert gas maybe any suitable inert gas such as argon, helium, neon, or anycombinations thereof. The inert gas may be flowed into the processchamber at a flow rate of about 100 sccm to about 10000 sccm, such asabout 1000 sccm to about 6000 sccm. The evacuation and/or purge gasremoves any remaining TMA or TEA or by-products from the processchamber. After the evacuation and/or purge, a second reactant agent,such as water (H₂O), ozone (O₃), hydrogen peroxide (H₂O₂), or any othersuitable oxidant, is pulsed into the process chamber. One or more secondreactant agent molecules bond with the aluminum layer to form analuminum oxide layer on a monolayer scale. The second reactant agent maybe flowed into the process chamber at a flow rate of about 10 sccm toabout 8000 sccm, such as about 300 sccm to about 5000 sccm, for exampleabout 500 sccm to about 2000 sccm. The evacuation and/or purge may beperformed again to remove by-products from the process chamber. Thesesteps may be repeated in successive cycles as the aluminum oxide isbuilt-up to the desired thickness on the surfaces of the barrier layer247 and the work-function tuning layer 244. For example, the aluminumoxide may have a thickness of about 1 Å to about 10 Å, for example about2 Å to about 5 Å, depending on the ALD cycles.

In some examples, a monolayer of silicon oxide is formed on the barrierlayer 247 of the FET in the first device region 250 a and on thework-function tuning layer 244 of the FET in the second device region250 b, respectively, by an ALD process. The ALD process begins withsetting the temperature of the semiconductor device 201 in a processchamber to a temperature range of about 20° C. to about 500° C., forexample about 200° C. to about 500° C. A first reactant agent, such assilanes or disilanes discussed above, is pulsed into the process chamberso that the semiconductor device 201 is soaked or immersed in thesilanes or disilanes. The silanes or disilanes may be flowed into theprocess chamber at a flow rate of about 10 sccm to about 3000 sccm, suchas about 300 sccm to about 1000 sccm, for example about 300 sccm toabout 1000 sccm. The pulse time may be about 1 second to about 300seconds to form a silicon layer at the surface of the barrier layer 247and the work-function tuning layer 244, respectively. For example, thepulse time may be about 10 seconds to about 60 seconds. In some cases,the pulse time may be about 5 seconds to about 90 seconds. In somecases, the pulse time may be about 30 seconds to about 120 seconds. Thepulse of the first reactant agent is followed by evacuation and/or apurge gas such as an inert gas. The inert gas may be any suitable inertgas such as argon, helium, neon, or any combinations thereof. The inertgas may be flowed into the process chamber at a flow rate of about 100sccm to about 6000 sccm, such as about 1000 sccm to about 3000 sccm. Theevacuation and/or purge gas removes any remaining silanes or disilanesor by-products from the process chamber. After the evacuation and/orpurge, a second reactant agent, such as water (H₂O), ozone (O₃),hydrogen peroxide (H₂O₂), or any other suitable oxidant, is pulsed intothe process chamber so that one or more second reactant agent moleculesbond with the silicon layer to form a silicon oxide layer on a monolayerscale. The pulse time of the second reactant agent may be about 1 secondto about 300 seconds. For example, the pulse time may be about 10seconds to about 60 seconds. In some cases, the pulse time may be about5 seconds to about 90 seconds. In some cases, the pulse time may beabout 30 seconds to about 120 seconds. The second reactant agent may beflowed into the process chamber at a flow rate of about 10 sccm to about8000 sccm, such as about 300 sccm to about 5000 sccm, for example about500 sccm to about 2000 sccm. The evacuation and/or purge may beperformed again to remove any remaining second reactant agent andby-products from the process chamber. These steps may be repeated insuccessive cycles as the silicon oxide is built-up to the desiredthickness on the surfaces of the barrier layer 247 and the work-functiontuning layer 244. For example, the silicon oxide may have a thickness ofabout 1 Å to about 10 Å, for example about 2 Å to about 5 Å, dependingon the ALD cycles.

In any case, the layers exposed to the pre-treatment process 253 (e.g.,barrier layer 247 and work-function tuning layer 244) of the FETs arecovered or passivated by a monolayer of aluminum oxide or silicon oxideafter the pre-treatment process 253. The monolayer of aluminum oxide orsilicon oxide is thin (e.g., less than to Å), and thus, may haveminimized impacts on the gap-filling performance and/or thresholdvoltage (Vt) of other layers in the trenches 230. When the semiconductordevice 201 leaves the process chamber (e.g., for the subsequent ALDdeposition of a metal layer), the monolayer of aluminum oxide or siliconoxide can be exposed to air which may further terminate the majority ofdangling bonds with hydroxyl groups (—OH) that can readily react duringthe subsequent ALD to form a metal liner layer. Therefore, the growthrate of the subsequently deposited metal liner layer may not depend on avarying substrate surface (e.g., of the barrier layer 247 orwork-function tuning layer 244). Instead, the pre-treated barrier layerand the work-function tuning layer provide the same starting surface forthe subsequent ALD for a metal liner layer. As a result, the loadingeffect for the subsequent ALD due to substrate dependent growth may bemitigated.

At operation 118, after the surfaces of the exposed layers (e.g.,barrier layer 247 in the trench 230 of the FET in the first deviceregion 250 a and the work-function tuning layer 244 in the trench 230 ofthe FET in the second device region 250 b) have been treated, a metalliner layer 255 is conformally deposited in the trenches 230 (e.g., ontreated surfaces 261, 263 of the barrier layer 247 and the work-functiontuning layer 244), as shown in FIG. 9. The metal liner layer 255 may befabricated from a material similar to the capping layer 245, forexample. For example, the metal liner layer 255 may be or include anitride, silicon nitride, carbon nitride, and/or aluminum nitride oftantalum and/or titanium; a nitride, carbon nitride, and/or carbide oftungsten; the like; or a combination thereof. In some examples, themetal liner layer 255 is TiN. In some examples, the metal liner layer255 is TaN. In some examples, the metal liner layer 255 is TiON. In someexamples, the metal liner layer 255 is TaON. While a single layer of themetal liner layer 255 is shown, it is contemplated that the metal linerlayer 255 may include one or more other layers described herein. Themetal liner layer 255 and any other layers deposited over the treatedsurfaces 261, 263 may also be used to set the value of the work functionof the gate electrode metal 257. The metal liner layer 255 is depositedby ALD in some examples, although in other examples, the metal linerlayer 255 may be deposited by PECVD, MBD, or any deposition technique.

In some embodiments, during the formation of the metal liner layer 255,the oxygen in the monolayer may also react with the precursor used forthe metal liner layer 255 and form a mixing layer between the metalliner layer 255 and the monolayer 251 (of aluminum oxide or siliconoxide). Insets 297, 299 in FIG. 9 are partially enlarged views showingone embodiment where the mixing layer 293, 295 is formed on themonolayer 251 in the first device region 250 a and the second deviceregion 250 b, respectively. Depending on the material of the metal linerlayer 255 and the monolayer, the mixing layer can be a compound oftitanium aluminum oxide (Al-Ox-Ti), for example. In addition, since theoxygen is purged out during the formation of the metal liner layer 255,the oxygen level in the monolayer may be lower than that before theformation of the metal liner layer 255.

Due to the pre-treatment process 253, the growth rate of the metal linerlayer 255 deposited by ALD on the barrier layer 247 and thework-function tuning layer 244 is almost identical because the samestarting surface (e.g., the treated surfaces 261, 263 having an aluminumoxide or silicon oxide monolayer) is provided for both the FET in thefirst device region 250 a and the FET in the second device region 250 b.As a result, metal liner layer 255 can have uniform thickness on thebarrier layer 247 and the work-function tuning layer 244. In addition,the incubation time of the metal liner layer 255 on the barrier layer247 and the work-function tuning layer 244 during the ALD is improveddue to the aluminum oxide or silicon oxide monolayer having hydroxylgroup (—OH) termination 265, which is believed to promote the chemicalreaction with one or more precursor of the ALD for forming the metalliner layer 255. For example, it has been observed that soaking thebarrier layer (e.g., TaN) in TEA (flowed at 600 sccm) for 15 secondswould result in the thickness of the metal liner layer (e.g., TiN)increased by about 46% as compared to the case where no soaking isperformed on the barrier layer; soaking the barrier layer (e.g., TaN) inTEA (flowed at 600 sccm) for to seconds would result in the thickness ofthe metal liner layer (e.g., TiN) increased by about 40% as compared tothe case where no soaking is performed on the barrier layer; and soakingthe barrier layer (e.g., TaN) in TEA (flowed at 600 sccm) for 5 secondswould result in the thickness of the metal liner layer (e.g., TiN)increased by about 32% as compared to the case where no soaking isperformed on the barrier layer. Similar growth patterns were alsoobserved on the work-function tuning layer. These observations show theincubation of the metal liner layer during the ALD is enhanced on thetreated surfaces 261, 263 by using Al-based pre-soak process. Hence,after depositing the metal liner layer 255, the metal liner layer 255 ison the monolayer of aluminum oxide or silicon oxide, in someembodiments.

At operation 120, after the metal liner layer 255 has been formed on thetreated surfaces 261, 263, a gate electrode metal 257 is formed over themetal liner layer 255 and filled the trenches 230 defined in the ILD 218for the replacement gate structures 212 a, 212 b. The gate electrodemetal 257 may overburden the trenches 230 to a predetermined thickness,as shown in FIG. 10. In various embodiments, the gate electrode metal257 may be or include a conductive material, such as aluminum (Al),copper (Cu), titanium (Ti), tantalum (Ta), titanium aluminum (AlTi),titanium aluminum nitride (TiAlN), titanium (Ti), titanium nitride(TiN), tantalum nitride (TaN), tantalum silicon nitride (TaN), tantalumaluminum (AlTa), tantalum (Ta), nickel silicide, cobalt silicide, TaC,titanium silicon nitride (TaSiN), tungsten (W), tungsten nitride (WN),molybdenum nitride (MoN), platinum (Pt), ruthenium (Ru), other suitableconductive materials, or a combination thereof. In some examples, thegate electrode metal 257 is tungsten. Depending upon the material of thelayer to be formed, the gate electrode metal 257 may be formed by CVD,PECVD, PVD, plating, ALD, and/or other suitable processes.

At operation 122, a planarization process, such as a CMP, may be used toplanarize a top surface of the semiconductor device 201. Theplanarization process may remove portions of the gate electrode metal257, the metal liner layer 255, the monolayer 251, the barrier layer247, the capping layer 245, the work-function tuning layer 244, and thegate dielectric layer 242 from that are above the top surface of the ILD218, as shown in FIG. 11. Upon completion of the planarization process,a fresh top surface 259 of the ILD 218 is exposed.

The semiconductor device 201 fabricated according to the flow chart 100may undergo further processing to form various features and regions. Forexample, subsequent processing may form various contacts/vias/lines andmultilayers of interconnect features (e.g., metal layers and interlayeror intermetal dielectrics) on the substrate 200 including thesemiconductor device 201, configured to connect the various features toform a functional circuit that may include one or more devices (e.g.,one or more semiconductor devices 201). The various interconnectionfeatures may employ various conductive materials including copper,tungsten, and/or silicide. In one example, a damascene and/or dualdamascene process may be used to form a copper related multilayerinterconnection structure. Furthermore, additional process steps may beimplemented before, during, and after the flow chart 100, and someoperations described above may be replaced or eliminated depending uponthe application.

While various embodiments discussed above mitigate the substratedependent loading by pre-treating exposed surfaces of a barrier layerand/or a work-function tuning layer to provide the same starting surfacefor the subsequent ALD, it has been observed that the substratedependent growth of the work function metals can instead be used fortuning the threshold voltage for n-FET or p-FET devices to achieve amultiple threshold voltage scheme. In some multi-Vt metal gates, asemiconductor device may include two or more device regions and eachdevice region may include a p-type device or n-type device. FIG. 12illustrates a simplified semiconductor device 1200 at an intermediatestage of processing showing portions of the gate structures in threedevice regions 1202, 1204, 1206. Each device region includes an n-typedevice. Each n-type device in the device regions 1202, 1204, 1206 has awork-function tuning layer 1208 disposed over a gate dielectric layer1210. A metal layer 1212, such as a work-function tuning layer for ap-type device, such as TiN, TaN, TiAlN, TiSiN, is often formed withdifferent thicknesses between the work-function tuning layer 1208 andthe gate dielectric layer 1210 to affect the work function for the metalgates. In the example shown in FIG. 12, the metal layer 1212 in thedevice region 1202 has a first thickness Ti; the metal layer 1212 in thedevice region 1204 has a second thickness T2 greater than the firstthickness Ti; and the metal layer 1214 in the device region 1206 has athird thickness T3 greater than the second thickness T2. Since the workfunction of metal gates depends in part on the conductivity of the metallayer 1212, providing the same metal layer 1212 with different thicknesscan effectively change and separate the work function of different metalgates in the device regions 1202, 1204, 1206. With scaling of FinFETdevices, however, multi-Vt tuning using different film thickness may notbe practical since the space for the metal layer can be reduced orlimited.

Various embodiments discussed herein provide multi-Vt tuning for n-typeor p-type devices without forming multilayers of film stacks between thework-function tuning layer and the gate dielectric layer. Instead, thework function of metal gates at different device regions can be adjustedby providing a different metal layer between the work-function tuninglayer and the gate dielectric layer for n-type or p-type devices. Sincesome work function materials can have very strong substrate dependentgrowth behavior, the composition and thickness of the work-functiontuning layer at different device regions may be changed due to adifferent metal layer disposed underneath the work-function tuninglayer. FIG. 13 illustrates a simplified semiconductor device 1300 at anintermediate stage of processing according to some embodiments. Thesemiconductor device 1300 may be a multi-threshold voltage IC device,such as the semiconductor device 201 discussed above. For clarity, onlya portion of the gate structure shown in the insets 1360, 1362, 1364will be discussed. Other elements of the semiconductor device 1300, suchas source/drain regions 213 a-c, gate spacers 220, isolation regions216, fins 202, and ILDs 218, etc., can be referred to the semiconductordevice 201 as discussed above with respect to FIG. 5.

In an embodiment, the semiconductor device 1300 has three device regions1302, 1304, 1306, and each device region includes an n-type device.Similar to the semiconductor device 201 discussed above, the n-typedevice in the device regions 1302, 1304, 1306 can be an n-type lowthreshold voltage (N-LVT) device, an n-type standard threshold voltage(N-SVT), or an n-type high threshold voltage (N-HVT) device, dependingupon the application. While the n-type device is discussed herein, it iscontemplated that the concept is also applicable to p-type device, suchas a p-type FinFET device. Each n-type device in the device regions1302, 1304, 1306 has a work-function tuning layer 1308 disposed over agate dielectric layer 1310. Similar to the work-function tuning layer244 discussed above, suitable examples of the work-function tuning layer1308 may include Ti, Al, TaAl, TaAlC, TiAlC, TiAlO, HfAl, TiAl, TaC,TaCN, TaSiN, Mn, Zr, or other suitable materials having a work functionranging between 3.9 eV and 4.3 eV. In an embodiment, the work-functiontuning layer 1308 is TiAlC. Similar to the gate dielectric layer 242,the gate dielectric layer 1310 may include or be silicon oxide, siliconnitride, a high-k dielectric material, multilayers thereof, or othersuitable dielectric material. In some embodiments, the gate dielectriclayer 1310 may be a metal oxide of or a metal silicate of hafnium (Hf),aluminum (Al), zirconium (Zr), lanthanum (La), magnesium (Mg), barium(Ba), titanium (Ti), lead (Pb), multilayers thereof, or a combinationthereof.

Metal layers 1312, 1314, 1316 are provided between the work-functiontuning layer 1308 and the gate dielectric layer 1310 in the respectivedevice region 1302, 1304, 1306 to tune the work function value for themetal gates. The metal layers 1312, 1314, 1316 may be TiN, TaN, TiAlN,TiSiN, a composite containing metal nitride (such as TiN—Si₃N₄, TSN), orany suitable metal, such as those used for the capping layer 245 and thebarrier layer 247 as discussed above. In an embodiment, the thickness“T4” of the metal layer 1312, the thickness “T5” of the metal layer1314, and the thickness “T6” of the metal layer 1316 are substantiallythe same, for example about 10 Å. In some examples, the thickness ofeach of “T4”, “T5” and “T6” may be in a range of about 5 Å to about 15Å, for example about 8 to about 12 Å. Unlike the semiconductor device1200 of FIG. 12 where the same metal layer 1212 is formed with variousthicknesses for n-FET multi-Vt tuning, the metal layers 1312, 1314, 1316can be chemically different from each other. In an example embodiment,the metal layer 1312 in the device region 1302 is TiN; the metal layer1314 in the device region 1304 is TaN; and the metal layer 1316 in thedevice region 1306 is TSN. Since the work-function tuning layer 1308(e.g., TiAlC) can have very strong substrate dependent growth behavior(meaning the composition and thickness of TiAlC is substrate dependent),the use of different metal layers at respective device regions 1302,1304, 1306 can result in the TiAlC to form with different filmproperties and thickness, which in turn changes the work function valueof the work-function tuning layer 1308. In some embodiments, thedifference between the thickness of TiAlC on TSN and the thickness ofTiAlC on TaN can be about 12% to about 15%, and the different betweenthe thickness of TIAlC on TiN substrate and the thickness of TiAlC onTaN can be about 28% to about 39%.

FIGS. 14A to 14C show X-ray photoelectron spectroscopy (XPS) spectra ofmain component of the TiAlC deposited on TSN, TaN, and TiN substrates.The measured photoelectron intensity in arbitrary unit (A.U) is plottedas function of the binding energy (B.E). XPS employs X-rays to ejectcore electrons of the atoms present on the surface of TiAlC. The kineticenergy of these electrons is measured to obtain the binding energy ofthe electrons of interest, such as Al, C, and Si. The TiAlC wasdeposited on TSN, TaN, and TiN substrates at a temperature of about 350°C. to about 420° C. and a chamber pressure of about 1 Torr to about 20Torr. As for aluminum (Al 2p) spectrum in FIG. 14A (meaning the peaks ofmeasured electrons of Al atoms were emitted from the shell 2p), TiAlCdeposited on TiN shows highest signal spectrum of Al (by subtracting abackground spectrum of about 1.8 from a measured spectrum of about 4.7),while TiAlC deposited on TaN and TiAlC deposited on TSN both show lowersignal spectrum of Al, meaning more aluminum is found in TiAlC whendeposited on TiN substrate. Therefore, TiAlC on TiN substrate can havemore positive charge carriers than TiAlC on TaN or TSN substrate due tohigher concentration of Al in TiAlC.

As for carbon (C is) spectrum in FIG. 14B (meaning the peaks of measuredelectrons of C atoms were emitted from the shell is), TiAlC deposited onTiN also shows highest signal spectrum of C (by subtracting a backgroundspectrum of about 4 from a measured spectrum of 7.3), while TiAlCdeposited on TaN and TiAlC deposited on TSN both show lower signalspectrum of C, meaning more carbon is found in TiAlC when deposited onTiN substrate.

As for silicon (Si 2p) spectrum in FIG. 14C (meaning the peaks ofmeasured electrons of Si atoms were emitted from the shell 2p), TiAlCdeposited on TaN shows highest signal spectrum of Si (by subtracting abackground spectrum of about 2.7 from a measured spectrum of 4.5), whileTiAlC deposited on TiN shows lowest signal spectrum of Si, meaning moresilicon is found in TIAlC when deposited on TaN substrate. Higher Siintensity found in TiAlC suggests the thickness of TiAlC on TaN isthinner than that of TIAlC on TiN since Si signal from the underlyingfin (e.g., fin 202) is easily detected.

The XPS spectra of FIGS. 14A to 14C indicate that providing differentsubstrates can result in different film properties and thickness ofTiAlC. Therefore, by using different metal layer at respective deviceregions 1302, 1304, 1306, TiAlC can be formed with distinguished filmproperties and thickness. The distinguished TiAlC films on differentsubstrates provide different n-type work functions for the purpose ofmulti-Vt tuning without stacking multilayers of the metal layer. As aresult, more space can be provided for filling metal gate or othersuitable work-function tuning layers for the device.

An example process of forming different metal layer in respective deviceregions 1302, 1304, 1306 may be performed as follows. After forming thegate dielectric layer 1310 in the trenches 1301, 1303, 1305 between thegate spacers in the device regions 1302, 1304, 1306, a first metal layer1312, such as TiN, is formed over the gate dielectric layer 1310 in thetrenches 1301, 1303, 1305 of the device regions 1302, 1304, 1306,respectively. A patterned mask, such as the patterned mask structure 248discussed above, is then disposed on the device region 1302 of thesemiconductor device 1300. The patterned mask overfills the trench andcovers the exposed surface of the device region 1302, while exposing thedevice regions 1304 and 1306 for further processing such as etching. Oneor more etch processes may then be performed to selectively remove themetal layer 1312 from the trenches of the device regions 1304 and 1306,leaving the first metal layer 1312 in the trench of the device region1302.

A second metal layer 1314, such as TaN, is then formed in the trenchesin the device regions 1302, 1304, 1306, respectively. Likewise, apatterned mask is disposed on the device region 1304 of thesemiconductor device 1300. One or more etch processes may then beperformed to selectively remove the metal layer 1314 from the trenchesof the device regions 1302 and 1306, leaving the second metal layer 1314in the trench of the device region 1304. Thereafter, a third metal layer1316, such as TSN, is formed in the trenches in the device regions 1302,1304, 1306, respectively. A patterned mask is disposed on the deviceregion 1306 of the semiconductor device 1300. One or more etch processesmay then be performed to selectively remove the metal layer 1316 fromthe trenches of the device regions 1302 and 1304, leaving the thirdmetal layer 1316 in the trench of the device region 1306. In this way,the first metal layer 1312 (e.g., TiN) can be formed in the deviceregion 1302 between the gate dielectric layer 1310 and the work-functiontuning layer 1308, the second metal layer 1314 (e.g., TaN) can be formedin the device region 1304 between the gate dielectric layer 1310 and thework-function tuning layer 1308, and the third metal layer 1316 (e.g.,TSN) can be formed in the device region 1306 between the gate dielectriclayer 1310 and the work-function tuning layer 1308. With this approach,the composition and thickness of the work-function tuning layer 1308(e.g., TiAlC) can be changed as needed for the purpose of multi-Vttuning.

After the work-function tuning layer 1308 has been formed on the metallayers 1312, 1314, 1316 in the respective device regions 1302, 1304,1306, processing on the semiconductor device 1300 may be proceed to forma metal liner layer and a gate electrode metal as discussed above withrespect to FIGS. 9 through 11. The semiconductor device 1300 may undergofurther processing to form various features and regions, such ascontacts/vias/lines and multilayers of interconnect features, that maybe required to form a functional integrated device.

Various embodiments described herein may offer several advantages. Itwill be understood that not all advantages have been necessarilydiscussed herein, no particular advantage is required for anyembodiment, and other embodiments may offer different advantages. As oneexample, embodiments discussed herein include methods and structuresdirected to a pre-deposition treatment process which includes soaking aparticular layer such as a work-function tuning layer, a barrier layer,a capping layer, other appropriate next metal layer, etc. that has beendeposited in a trench of a FET (e.g., for the SVT device) and a trenchof another FET (e.g., for the uLVT device) in a reactant agent toprovide a treated surface prior to deposition of a subsequent metalliner layer over the treated surface of the particular layer. In variousembodiments, the pre-deposition treatment process forms a monolayer ofthe reactant on the treated surface. The monolayer of the reactant canbe oxidized by exposing to an external ambient or any suitable oxidantswhich terminates the treated surface with hydroxyl group (—OH) that canreadily react with the subsequent metal liner layer. By employing thepre-deposition treatment process, the work function of the subsequentlydeposited metal liner layer may not depend on the quality of anunderlying surface (e.g., such as an underlying work-function tuninglayer having an oxidized surface layer). In addition, the growth rate ofthe subsequently deposited metal liner layer may not depend on a varyingsubstrate surface of the particular layer that can affect the growthrate (and thus the thickness) of the subsequently deposited metal linerlayer. Instead, the treated surface of the particular layer having amonolayer of the reactant provides generally the same starting surfacefor the subsequent metal liner layer deposition. Furthermore, themonolayer of the reactant can be thin (e.g., less than 10 Å), and thus,can have minimized impacts on the gap-filling performance and/orthreshold voltage (Vt) of other layers in the trenches. As a result, theloading effect for the subsequent metal liner layer due to substratedependent growth can be mitigated.

Other advantages may include multi-Vt tuning for n-type or p-typedevices by providing different or distinct metal layer between thework-function tuning layer and the gate dielectric layer for differentdevice regions of a FET, such as an n-FET or p-FET device. The distinctmetal layer can affect the composition and thickness of thework-function tuning layer, thereby changing the work function value ofthe work-function tuning layer deposited thereon. The distinguishedwork-function tuning layers (e.g., TiAlC) on different substratesprovide different n-type work functions for the purpose of multi-Vttuning without stacking multilayers of the metal layer. As a result,more space can be provided for filling metal gate or other suitablework-function tuning layers for the device.

In one embodiment, a method for semiconductor processing is provided.The method includes exposing a first metal-containing layer of a firstdevice and a second metal-containing layer of a second device to areactant to form respective monolayers on the first metal-containinglayer and the second metal-containing layer, the first device and thesecond device being on a substrate, the first device comprising a firstgate structure including the first metal-containing layer, the seconddevice comprising a second gate structure including the secondmetal-containing layer, the first metal-containing layer being adifferent material from the second metal-containing layer. The methodalso includes exposing the monolayers on the first metal-containinglayer and the second metal-containing layer to an oxidant to provide ahydroxyl group (—OH) terminated surface for the monolayers on the firstmetal-containing layer and the second metal-containing layer, andforming a third metal-containing layer on the —OH terminated surfaces ofthe monolayers on the first metal-containing layer and the secondmetal-containing layer.

Another embodiment is a semiconductor device. The semiconductor deviceincludes a substrate, and a first device having a first gate structureover the substrate. The first gate structure includes a gate dielectriclayer over the substrate, a barrier layer over the gate dielectriclayer, a monolayer of aluminum oxide or silicon oxide on the barrierlayer, a metal liner layer over the monolayer of aluminum oxide orsilicon oxide on the barrier layer, and a gate electrode metal over themetal liner layer.

In one yet embodiment a method is provided. The method includes forminga gate dielectric layer in a first trench and a second trench, the firsttrench and the second trench each being defined in a dielectricstructure and intersecting a respective fin on a substrate, forming afirst metal layer over the gate dielectric layer in the first trench,forming a second metal layer over the gate dielectric layer in thesecond trench, wherein the first metal layer and the second metal layerare chemically different from each other, forming a work-function tuninglayer directly on the first metal layer in the first trench and thesecond metal layer in the second trench, respectively, the work-functiontuning layer having a different thickness on the first metal layer thanthe second metal layer, and forming respective gate electrodes over thework-function tuning layer in the first trench and the second trench.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

The invention claimed is:
 1. A semiconductor device comprising: asubstrate; and a first device having a first gate structure over thesubstrate, wherein the first gate structure comprises: a first gatedielectric layer over the substrate; a first barrier layer over thefirst gate dielectric layer; a first monolayer of aluminum oxide orsilicon oxide on the first barrier layer; a first metal liner layer overthe first monolayer of aluminum oxide or silicon oxide on the firstbarrier layer; and a first gate electrode metal over the first metalliner layer.
 2. The semiconductor device of claim 1 further comprising:a second device having a second gate structure over the substrate,wherein the second gate structure comprises: a second gate dielectriclayer over the substrate; a second barrier layer over the second gatedielectric layer; a work-function tuning layer over the second barrierlayer; a second monolayer of aluminum oxide or silicon oxide on thework-function tuning layer; a second metal liner layer over the secondmonolayer of aluminum oxide or silicon oxide on the work-function tuninglayer; and a second gate electrode metal over the second metal linerlayer.
 3. The semiconductor device of claim 2, wherein a thickness ofthe first metal liner layer in the first gate structure is substantiallythe same as a thickness of the second metal liner layer in the secondgate structure.
 4. The semiconductor device of claim 2, wherein thework-function tuning layer and the second barrier layer are differentmaterials.
 5. The semiconductor device of claim 2, wherein the firstdevice and the second device are different type devices selected from agroup comprising: an n-type ultra-low threshold voltage (N-uLVT) device,an n-type low threshold voltage (N-LVT) device, an n-type standardthreshold voltage (N-SVT), an n-type high threshold voltage (N-HVT)device, a p-type ultra-low threshold voltage (P-uLVT) device, a p-typelow threshold voltage (P-LVT) device, a p-type standard thresholdvoltage (P-SVT), and a p-type high threshold voltage (P-HVT) device. 6.The semiconductor device of claim 1 further comprising first gatespacers along opposing sides of the first gate structure, wherein thefirst gate dielectric layer of the first gate structure extends alongsidewalls of the first gate spacers.
 7. The semiconductor device ofclaim 1 further comprising a first capping layer interposed between thefirst gate dielectric layer and the first barrier layer.
 8. Asemiconductor device comprising: a substrate; and a first device havinga first gate structure over the substrate, wherein the first gatestructure comprises: a first gate dielectric layer over the substrate; afirst barrier layer over the first gate dielectric layer; a firstmonolayer of a first material on the first barrier layer, wherein thefirst material comprises aluminum oxide or silicon oxide; a first metalliner layer over the first monolayer of the first material; and a firstgate electrode metal over the first metal liner layer; and a seconddevice having a second gate structure over the substrate, wherein thesecond gate structure comprises: a second gate dielectric layer over thesubstrate; a second barrier layer over the second gate dielectric layer;a second work-function tuning layer over the second barrier layer; asecond monolayer of the first material on the second work-functiontuning layer; a second metal liner layer over the second monolayer ofthe first material, wherein the first metal liner layer and the secondmetal liner layer comprise a same material; and a second gate electrodemetal over the second metal liner layer.
 9. The semiconductor device ofclaim 8, wherein the first metal liner layer and the second metal linerlayer have a same thickness.
 10. The semiconductor device of claim 8,wherein the first barrier layer and the second work-function tuninglayer comprises different materials.
 11. The semiconductor device ofclaim 8 further comprising one or more additional first monolayers ofthe first material directly on the first monolayer of the firstmaterial, and further comprising one or more additional secondmonolayers of the first material directly on the second monolayer of thefirst material.
 12. The semiconductor device of claim 11, wherein acombined thickness of the first monolayer of the first material and oneor more additional first monolayer of the first material is betweenabout 2 Å to about 5 Å.
 13. A semiconductor device comprising: asubstrate; and a first device having a first gate structure over thesubstrate, wherein the first gate structure comprises: a first gatedielectric layer over the substrate; a first metal layer over the firstgate dielectric layer; a first layer of aluminum oxide or silicon oxidedirectly on the first metal layer; a second metal layer directly on thefirst layer of aluminum oxide or silicon oxide; and a first gateelectrode metal over the second metal layer; and a second device havinga second gate structure over the substrate, wherein the second gatestructure comprises: a second gate dielectric layer over the substrate;a third metal layer over the second gate dielectric layer; a secondlayer of aluminum oxide or silicon oxide directly on the third metallayer; a fourth metal layer directly on the second layer of aluminumoxide or silicon oxide, wherein the second metal layer and the fourthmetal layer comprise a first material, wherein the first metal layer andthe third metal layer comprise different materials; and a second gateelectrode metal over the fourth metal layer.
 14. The semiconductordevice of claim 13, wherein a thickness of the second metal layer issubstantially equal to a thickness of the fourth metal layer.
 15. Thesemiconductor device of claim 13, wherein the first device and thesecond device have a same conductivity type.
 16. The semiconductordevice of claim 15, wherein the first device and the second device havedifferent threshold voltages.
 17. The semiconductor device of claim 13,wherein the first device further comprises a fifth metal layerinterposed between the first metal layer and the first gate dielectriclayer, wherein the second device further comprises a sixth metal layerinterposed between the third metal layer and the second gate dielectriclayer, wherein the fifth metal layer and the sixth metal layer are asame material.
 18. The semiconductor device of claim 13, wherein thefirst material comprises TiN, TaN, TiON, or TaON.
 19. The semiconductordevice of claim 13, wherein the first layer of aluminum oxide or siliconoxide comprises one or more monolayers of aluminum oxide or siliconoxide.
 20. The semiconductor device of claim 13, wherein the first layerof aluminum oxide or silicon oxide comprises a single monolayer ofaluminum oxide or silicon oxide.